Dyestuffs of the oxazine series and a process of preparing them



Patented Apr. 26, 1938 UNITED STATES PATENT OFFICE DYESTUFFS OF THE OXAZENE SERIES AND A PROCESS OF PREPARING- THEM Georg Kranzlein, Heinrich Greune, and Max Thiele, Frankfort-on-the-Main, Germany, assignors to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application October 26, 1934, Se-

rial No. 750,202. In Germany June 6, 1928 9 Claims.

wherein X stands for hydrogen or halogen, Y stands for hydrogen or alkyl and the Rs stand for aromatic groups of the benzene or naphthalene series, having at least one unsubstituted position adjacent to the NH-groups, the Ris stand for aromatic groups of the benzene, diphenyl or naphthalene series and wherein the two 'R1NR-chains are identical, yield, when being heated as such alone or with the addition of an oxidizing agent and, if necessary, of a catalyst, in a high-boiling solvent, bluish condensation products, from which, by sulfonation, water-soluble dyestuffs are obtained which dye the fiber valuable blue, bluish-gray or bluishgreen tints.

To perform the reaction there may be used as high-boiling solvents nitrobenzene, trichlorobenzene or the like, as ,oxidizing agents potassium ferricyanide, pyrolusite, ferric chloride or similar products and as catalysts there may be used phosphorus pentachloride, antimony pentachloride and others more. The sulfonation may preferably be carried out by means of fuming sulfuric acid or concentrated sulfuric acid.

Instead of first condensing and then introducabove stated it is, of course, also possible to introduce the sulfo group already before the oxazine has been formed, by starting, for instance, from,

ing the sulfo group by a subsequent operation as for instance, those which have the following constitution wherein Z means that the dyestuff may be sulfonated, X stands for hydrogen or halogen, Y means hydrogen or alkyl and R represents an aromatic group of the benzene or napthalene series, the position of the sulfo group being undetermined. R1 for an aromatic group of the benzene, diphenyl or naphthalene series, and wherein the two R1NRchains are identical.

Both by their excellent fastness to light and their remarkable shades these new blue, bluishgray and bluish-green dyestuffs are particularly valuable for dyeing silk.

When reacting upon the said new sulfonated dyestuffs in the manner indicated in U. S. Patent No. 1,800,299 with the bases characterized in the said patent, blue, bluish-gray and bluish-green dye pigments are obtained which are very suitable as nitrocellulose (varnish) cellonand alcohol lacquers.

The following examples serve to illustrate the invention but they are not intended to limit it thereto, the parts being by weight:

(1) parts of 2.5-di(-para-aminodiphenylamino) -3.6-dichloro-lA-berizoquinone are heated to boiling temperature for 8 hours with 12 parts of phosphorus pentachloride and 5 parts of pyrolusite in 1000 parts of nitrobenzene. After cooling, the separated condensation product is filtered by suction, subsequently washed with alcohol and dried.

It forms a crystalline powder showing aviolet luster on its surface, is insoluble in water, somewhat soluble in-benzene to a reddish-violet solu- .tion, sparingly soluble in alcohol to a blue and in nitrobenzene to a brownish-violet solution. By sulfonating it by means of sulfuric acid or fuming sulfuric acid, a sulfonic acid is obtained which dyes silk and wool blue tints of very good fastness to light and which has also in aqueous or soda alkaline solution a' great afinity for the ordinary or previously mordanted textile fiber,

The 2.5di(-para -aminopheriy1ami'no) -3.6-dichloro-lA-benzoquinone used as starting ma-. terial may be prepared by condensing chloranil with para-amino-diphenylamine in the presence of alcohol. It forms a blackish-brown powder melting at a temperature of about 300 C., being insoluble in alcohol and glacial acetic acid, sparingly soluble in ortho-dichlorobenzene.

Instead of para-aminodiphenylamine there may also be used para-amino-N-methyldiphenylamine, meta aminodiphenylamine, amino- 7 phenyl-alphaenaphthylamine,aminophenylbetaquinoneob-tainable by condensation of para? materials which have been prepared bymeajns of naphthylamine, aminonaphthylphenylamine, aminodinaphthylamineor the like. V

forms a bluish black powder. water and dissolves in concentrated sulfuric acid to an olive-green solution. It dissolves in hot trichlorobenzene to a violet solution, having a brown fluorescence. By sulfonating the product in concentrated suliuric,. acid, a sulfonic acid is obtained which dyes silk, wool, cotton, viscose artificial fiber and paper fast bluish-gray tints.

(3)" '100 'parts of 2.5-di(-para-amino-ortho- V methcxydiphenylamine) -3.6-dichloro-1.4-benzoaminororthofmethoxydiphenylamine with ch10- roanil are 'boiled for 3 hoursiin l500 parts of nitrobnzene. lgn orderto remove the nitrobenz eneysteam is then introduced, the remaining residue is filtered'off and: dried. It forms a darkviolet powder which dissolvesin concentrated sulfuricacid'to a green solution. It is sparingly soluble in organic solvents. .It dissolvesa little in trichlorobenzene to a blue solution, havinga red fluorescence. 7

When sulfonated in str'ongsulfuric acid, the 7 reaction productlyieldsg-a dyestuff-sulfonic acid fwhich dyes silk, wool, cotton and viscose artificial fiber etc. blue tints pr fastness to light.

; (4) 100 parts of'2.5-di(-para-amino-[para] V phenyl] diphenylamine) -3.6-dichloro-1.4-benzo "quinone obtainable by condensation of para- ,amino- (paraphenyl) -diphenylamine with chlori'anil in alcoholare boiled for. 5' hours in 1000 parts of'nitrobenzene. After cooling of the reaction mass, the solvent removed by introduc-j 7 tion of steam, the distillation residue isolated by filtration and dried. s v r The reaction product forms a dark violet'powder which isl sparinglysolublein organic solvents and shows a red fluorescence intrichlorobenzene.

. It dissolves in concentrated sulfuric acid to an 1 oliveegreen solution. 'By sulfonation iniconcem trated sulfuric acid'or fumingsulfuric acid; a

' 'sulfonic acid is obtained which dyes ,Wool, silk,

cotton,lviscose artificial"fiber etcf blue tints of good fastness tolig'ht; r p 7 1 Similar dyestuffs are obtained by parent.

' 'sisting of hydrogen and halogen, Y-for a radical of the group consisting of hydrogen and'a'lkyl, R foranaromatic group offthe benzene'or naph-- thalene series, R1 for an aromatic group of the 'agroups stand inxpi 05 position an d the mitotic] 1.4-ben'zoquinone instead of chlora'nil, andtreating them as described inthe foregoing examples. We claim 2' s V 7 1. The process which comprises boiling in the presence of nitrobenzene and a small. amount of 5 phosphorus pentachloride and pyrolusite 2.5-di- (-para-amino-diphenylamino) 3.6 -dichloro--1.4-

benzoquinone.

7 2. The process which comprises boiling in the presence of nitrobenzene anda smallamount of 10 phosphorus pentachloride. and pyrolusite 2.5- di (-para amino diphenylaQmino) -3.6-dichloro- 'lA-btenzoduinbne and then sulfronating the prod-' uct thus obtained.

3. A compound selected sisting of the compounds ofthe general formula:

wherein X stands. for a radical of the groupconbenzene, diphenyl or; naphthalene 'series' and whereinthe two R1N+R-chains are identical and the sulfonic acid of these compounds: f 7 V 4:. The compounds of: the' 'general' formulai I r ,7 40 wherein Z means that the compounds contain ,sulfo groups, X stands for a radical of the group consisting of hydrogen and halogen, Y for a radical of the group consisting of hydrogen and .alkyl', R and Ri'ior an aromatic'group of the benzene 'or naphthalene seriesQand wherein the two R1-NRchains are identical, dyingwbolarid: silk clear tints of good fastness to light. e

5. A'compound selected from the 'groupcon sisting of the compounds ofthe general formula... :5

" X it wherein X stands for a radical of the group con-5;: 7 7 sisting of hydrogen and halogemY for a radical V 1 of the groupconsisting. of fhydrogen and alkyl and wher'einthe i I g acids of these compounds. A s

6. The compounds of; the general formulazfl r p, r X

from the group con-- '15 wherein Z means that the compounds contain sulfo groups, X stands for a radical of the group consisting of hydrogen and halogen, Y for a radical of the group consisting of hydrogen and alkyl and wherein the groups stand in 111 or m position, dyeing wool and silk clear tints of good fastness to light.

8. The compound of the formula:

wherein Z means that the dyestuff contains sulfo groups, dyeing silk, wool, cotton, viscose artificial fiber and paper fastblue gray tints.

9. The compound of the formula:

7. The compound of the formula:

z O U O EN 0 N wherein Z means that the dyestufi contains sulfo groups, dyeing silk and wool blue tints of good 35 fastness to light.

wherein Z means that the dyestufi contains sulfo groups, dyeing wool, silk, cotton, viscose artificial fiber, etc. blue tints of good fastness to light.

GEORG KRANZLEIN. HEINRICH GREUNE. MAX TI-IIELE. 

